Regulating the Chiroptical Expression of Aggregated Solvophobic Core by Solvophilic Segments.

The investigation of chiral supramolecular stacking is of essential significance for the understanding of the origin of homochirality in nature. Unlike structurally well-defined amphiphilic liposomes, it remains unclear whether the solvophilic segments of the amphiphilic block copolymer play a decisive role in the construction of asymmetric superstructures. Herein, insights are presented into the stacking patterns and morphological regulation in azobenzene-containing block copolymer assemblies solely by modulating the solvophilic chain length. The solvophilic poly(methacrylic acid) (PMAA) segments of different molecular weights could cause multi-mode chirality inversions involving stacking transitions between intra-chain π-π stacking, inter-chain H- and J-aggregation. Furthermore, the length of the solvophilic PMAA also affects the morphology of the chiral supramolecular assemblies; rice grain-like micelles, worms, nanofibers, floccules, and lamellae can be prepared at different solvophilic-solvophobic balance. The comprehensive mechanism is collectively revealed by utilizing various measurement methods, such as including circular dichroism (CD), small-angle X-ray scattering (SAXS), and wide-angle X-ray diffraction (WAXD). This study highlights the critical importance of fully dissolved solvophilic segments for the chiroptical regulation of the aggregated core, providing new insights into the arrangement of chiral supramolecular structures in polymer systems.

Quaternary ammonium salts for water treatment with balanced rate of sterilization and degradation.

The growing number of infections caused by drug-resistant bacteria which arise from the overuse of antibiotics has severely affected the normal operation of human society. The high antibacterial activity of QAS makes it promising as an alternative to antibiotics, but it suffers from secondary pollution due to its non-degradation. Here we have synthesized a class of gemini quaternary ammonium salts (GQAS) with different carbon chain lengths containing ester groups by using facile methylation reaction. Quaternary ammonium groups contribute to insert negatively charged bacterial membranes, resulting in membrane damage and bacteria death. Compared with conventional single-chain QAS, except for the more efficient antibacterial efficiency attribute to the presence of the second carbon chain, GQAS with alterable antibacterial properties can minimize the possibility of bacterial resistance and reduce the accumulation of GQAS in the environment through the introduction of degradable ester groups. GQAS is completely superior to the commercial bactericide benzalkonium chloride (BAC) in both antibacterial activity and degrade performance, which can be used as a more environmentally friendly bactericide.

Simultaneous Chiral Fixation and Chiral Regulation Endowed by Dynamic Covalent Bonds.

The construction of chiral superstructures through the self-assembly of non-chiral polymers usually relies on the interplay of multiple non-covalent bonds, which is significantly limited by the memory ability of induced chirality. Although the introduction of covalent crosslinking can undoubtedly enhance the stability of chiral superstructures, the concurrent strong constraining effect hinders the application of chirality-smart materials. To address this issue, we have made a first attempt at the reversible fixation of supramolecular chirality by introducing dynamic covalent crosslinking into the chiral self-assembly of side-chain polymers. After chiral induction, the reversible [2+2] cycloaddition reaction of the cinnamate group in the polymer chains can be further controlled by light to manipulate inter-chain crosslinking and decrosslinking. Based on this photo-programmable and dynamic chiral fixation strategy, a novel pattern-embedded storage mechanism of chiral polymeric materials was established for the first time.

Switchable Phase Helicity Independent of the Absolute Configuration of the Stereocenter: Anomalous Induction between Sergeants and Soldiers in Chiral Liquid-Crystalline Polymers.

Controlling the secondary phase in chiral liquid-crystalline (LC) polymers is of great importance since it transfers and amplifies molecular information to the macroscopic properties. However, the chiral superstructures of the LC phase are determined exclusively by the inherent configuration of the parent chiral source. Here, we report the switchable supramolecular chirality of heteronuclear structures by the untraditional command between common chiral "sergeant" units and various achiral "soldier" units. Different chiral induction pathways between sergeants and soldiers were observed for copolymer assemblies with mesogenic and non-mesogenic soldier units, demonstrating the formation of a helical phase independent of the absolute configuration of the stereocenter. In the presence of non-mesogenic soldier units, the classical SaS (Sergeants and Soldiers) effect in the amorphous phase was observed; whereas in a full LC system, bidirectional command of sergeants was activated in response to the phase transition. Meanwhile, a full spectrum of morphological phase diagrams including spherical micelles, worms, nanowires, spindles, tadpoles, anisotropic ellipsoidal vesicles, and isotropic spherical vesicles were successfully achieved. Such spindles, tadpoles, and anisotropic ellipsoidal vesicles have rarely been obtained previously from chiral polymer systems.

Quaternary Ammonium Salts: Insights into Synthesis and New Directions in Antibacterial Applications.

The overuse of antibiotics has led to the emergence of a large number of antibiotic-resistant genes in bacteria, and increasing evidence indicates that a fungicide with an antibacterial mechanism different from that of antibiotics is needed. Quaternary ammonium salts (QASs) are a biparental substance with good antibacterial properties that kills bacteria through simple electrostatic adsorption and insertion into cell membranes/altering of cell membrane permeability. Therefore, the probability of bacteria developing drug resistance is greatly reduced. In this review, we focus on the synthesis and application of single-chain QASs, double-chain QASs, heterocyclic QASs, and gemini QASs (GQASs). Some possible structure-function relationships of QASs are also summarized. As such, we hope this review will provide insight for researchers to explore more applications of QASs in the field of antimicrobials with the aim of developing systems for clinical applications.

Adsorption of Phenanthrene on Multi-Walled Carbon Nanotubes in the Presence of Nonionic Surfactants.

The bioavailability and mobility of phenanthrene (Phe) adsorbed by multi-walled carbon nanotubes (MWCNTs) may be substantially influenced by nonionic surfactants used both in the synthesis and dispersion of MWCNTs. The adsorption mechanisms of Phe adsorbed onto MWCNTs under the different nonionic surfactants Tween 80 (TW-80) and Triton X-100 (TX-100) in the aqueous phase were investigated in terms of changes in the MWCNTs' compositions and structures. The results showed that TW-80 and TX-100 were easily adsorbed onto MWCNTs. Phe adsorption data onto MWCNTs were better suited to the Langmuir equation than the Freundlich equation. Both TW-80 and TX-100 reduced the adsorption capacity of Phe onto MWCNTs. When TW-80 and TX-100 were added in the adsorption system, the saturated adsorption mass of Phe decreased from 35.97 mg/g to 27.10 and 29.79 mg/g, respectively, which can be attributed to the following three reasons. Firstly, the hydrophobic interactions between MWCNTs and Phe became weakened in the presence of nonionic surfactants. Secondly, the nonionic surfactants covered the adsorption sites of MWCNTs, which caused Phe adsorption to be reduced. Finally, nonionic surfactants can also promote the desorption of Phe from MWCNTs.

Porous boron nitride intercalated zero-valent iron particles for highly efficient elimination of organic contaminants and Cr (VI).

Developing novel bifunctional materials to high efficiently degrade organic pollutants and eliminate hexavalent chromium (Cr (VI)) is significantly desired in the wastewater treatment field. The porous boron nitride (p-BN) was fabricated by a two-stage calcination strategy and was innovatively employed to support zero-valent iron (ZVI), achieving the bifunctional material (p-BN@ZVI) to degrade carbamazepine (CBZ) and eliminate Cr (VI). p-BN@ZVI could degrade more than 98% CBZ in 6 min with the high apparent first-order constant (kobs) of 0.536 min-1, almost 5 times higher than that of the ZVI/PMS system and outperformed most previous reported ZVI supported catalysts, which was mainly ascribed to the fact that the introduction of p-BN with high surface area (793.97 m2/g) improved the dispersion of ZVI and exposed more active sites. Quenching tests coupled with electron paramagnetic resonance (EPR) suggested that •OH was the major reactive oxygen species with a contribution of 71.6%. Notably, the p-BN@ZVI/PMS system expressed low activation energy of 8.23 kJ/mol and reached a 65.69% TOC degradation in 20 min even at 0 °C. p-BN@ZVI possessed remarkable storage stability and could still degrade 92.3% CBZ despite three-month storage. More interestingly, p-BN@ZVI was capable to eliminate 98.1% of 50 mg/L Cr (VI) within 5 min through adsorption and reduction, where nearly 80% Cr (VI) was transformed to Cr (III), and exhibited the maximum Cr (VI) elimination capacity of 349 mg/g. This study provides new insights into the efficient organic contaminants degradation and Cr (VI) elimination in the treatment of wastewater.

Case Report: Preemptive Treatment With Low-Dose PD-1 Blockade and Azacitidine for Molecular Relapsed Acute Myeloid Leukemia With RUNX1-RUNX1T1 After Allogeneic Hematopoietic Stem Cell Transplantation.

Acute myeloid leukemia (AML) patients who develop hematological relapse (HR) after allogeneic hematopoietic stem cell transplantation (allo-HSCT) generally have dismal clinical outcomes. Measurable residual disease (MRD)-directed preemptive interventions are effective approaches to prevent disease progression and improve prognosis for molecular relapsed patients with warning signs of impending HR. In this situation, boosting the graft-vs-leukemia (GVL) effect with immune checkpoint inhibitors (ICIs) might be a promising prevention strategy, despite the potential for causing severe graft-vs-host disease (GVHD). In the present study, we reported for the first time an AML patient with RUNX1-RUNX1T1 who underwent preemptive treatment with the combined application of tislelizumab (an anti-PD-1 antibody) and azacitidine to avoid HR following allo-HSCT. On day +81, molecular relapse with MRD depicted by RUNX1-RUN1T1-positivity as well as mixed donor chimerism occurred in the patient. On day +95, with no signs of GVHD and an excellent eastern cooperative oncology group performance status (ECOG PS), the patient thus was administered with 100 mg of tislelizumab on day 1 and 100 mg of azacitidine on days 1-7. After the combination therapy, complete remission was successfully achieved with significant improvement in hematologic response, and the MRD marker RUNX1-RUNX1T1 turned negative, along with a complete donor chimerism in bone marrow. Meanwhile, the patient experienced moderate GVHD and immune-related adverse events (irAEs), successively involving the lung, liver, lower digestive tract and urinary system, which were well controlled by immunosuppressive therapies. As far as we know, this case is the first one to report the use of tislelizumab in combination with azacitidine to prevent post-transplant relapse in AML. In summary, the application of ICIs in MRD positive patients might be an attractive strategy for immune modulation in the future to reduce the incidence of HR in the post-transplant setting, but safer clinical application schedules need to be explored.

Case Report: Asymmetric Bone Marrow Involvement in Patients With Acute Leukemia After Allogeneic Hematopoietic Stem Cell Transplantation.

After allogeneic hematopoietic stem cell transplantation (allo-HSCT), acute leukemia relapse is common, and asymmetric bone marrow recurrence hasn't been reported. Because the anatomical distribution of acute leukemia clones in the bone marrow after allo-HSCT is presumed to be diffuse, bone marrow aspirations are performed in single site. The first case was a 20-year-old man who was diagnosed with acute myelomonocytic leukemia and received haploidentical allo-HSCT. Routine bone marrow biopsy of his left posterior iliac bone marrow showed 52% leukemia blasts, while the right side had 0% blasts 10 days later. The second case was a 23-year-old woman who was diagnosed with acute B lymphoblastic leukemia and received HLA-identical sibling allo-HSCT. Although 62% of blasts were found in her left iliac marrow on day +122, 0% of blasts were found on a sample obtained from the right iliac crest on day +128. Bilateral iliac bone marrow pathology and whole-body 18F-FDG PET/CT scans confirmed that the leukemic infiltration in her bone marrow was asymmetric. To our knowledge, these are the first case reports of asymmetric bone marrow infiltration of blasts in acute leukemia patients after allo-HSCT. Bilateral posterior iliac crest aspirations or 18F-FDG-PET/CT scans may help distinguish such involvement.

Redox-Mediated Disassembly to Build Activatable Trimodal Probe for Molecular Imaging of Biothiols.

Activatable multimodal probes that show enhancement of multiplex imaging signals upon interaction with their specific molecular target have become powerful tools for rapid and precise imaging of biological processes. Herein, we report a stimuli-responsive disassembly approach to construct a redox-activatable fluorescence/19F-MRS/1H-MRI triple-functional probe 1. The small molecule probe 1 itself has a high propensity to self-assemble into nanoparticles with quenched fluorescence, attenuated 19F-MRS signal, and high 1H-MRI contrast. Biothiols that are abundant in reducing biological environment were able to cleave the disulfide bond in probe 1 to induce disassembly of the nanoparticles and lead to fluorescence activation (∼70-fold), 19F-MRS signal amplification (∼30-fold) and significant r1 relaxivity reduction (∼68% at 0.5 T). Molecular imaging of reducing environment in live cells and in vivo was realized using probe 1. This approach could facilitate the development of other stimuli-responsive trimodal probes for molecular imaging.